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Lecture 7

Carbohydrates

Carbohydrates
They are important for
Formula=
Three major classes of carbohydrates:

Carbohydrates
They are important for energy storage, cell-cell signaling and cell wall structures.
Most have the formula (CH2O)n
Three major classes of carbohydrates: mono, oligo, poly saccharides
Monosaccharides are single sugars and can be divided into 2 groups: aldoses, which have
aldehyde groups, and ketoses, which have ketone groups.

R1
C
R2

O

Aldehyde is a carbonyl (C=O) where  One R grp is H
Ketone is a carbonyl where No R grp is H

Terminology .

Aldoses .

Ketoses .

D and L Solid wedge-shaped bonds point toward the reader. dashed wedges point away. .

Epimers

D-Glucose

and two of its epimers are shown as projection formulas. Each epimer differs from D-glucose in the configuration
at one chiral center (shaded pink).

Formation of hemiacetals and hemiketal

An aldehyde or ketone can react with an alcohol in a 1:1 ratio to yield a hemiacetal or hemiketal, respectively, creating a
new chiral center at the carbonyl carbon. Substitution of a second alcohol molecule produces an acetal or ketal. When
the second alcohol is part of another sugar molecule, the bond produced is a glycosidic bond.

Rings
In aqueous solution, monosaccharides with
five or more C atoms in the backbone occur
as cyclic (ring) structures in which the
carbonyl group has formed a covalent bond
with the O of a hydroxyl group along the
chain.
These 6-membered ring compounds are
called pyranoses.
These rings form due to a general reaction
that occurs between alcohols and
aldehydes or ketones to form derivatives
called
hemiacetals or hemiketals.
Anomers are isomeric forms of
monosaccharides that differ only in their
configuration about the hemiacetal
or hemiketal C.

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Phosphoester .

The reaction with Cu2+ is complex. yielding a mixture of products .Sugars are reducing agents Oxidation of the anomeric carbon of glucose under alkaline conditions.

yielding a mixture of products . Oxidation of the anomeric carbon of glucose under alkaline conditions. reduction is electron gain Reducing agent is electron donor. Gain of an electron by atom/molecule is called reduction. loss of electron is oxidation. The reaction with Cu2+ is complex. oxidising agent is electron acceptor.Sugars are reducing agents Oxidation is electron loss.

Because mutarotation interconverts the a and b forms of the hemiacetal. the bonds at this position are sometimes depicted with wavy lines. shown here as an illustration. with elimination of H2O and formation of a glycosidic bond.Glycosidic bond Disaccharide is formed from two monosaccharides (here. two molecules of Dglucose) when an —OH (alcohol) of one glucose molecule (right) condenses with the intramolecular hemiacetal of the other glucose molecule (left). The maltose molecule. as shown here. The reversal of this reaction is hydrolysis— attack by H2O on the glycosidic bond. retains a reducing hemiacetal at the C-1 not involved in the glycosidic bond. . to indicate that the structure may be either a or b.

Common Disaccharides .

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  two or many different  monosaccharides .Polysaccharides Polysaccharides can have one.

Amylose and glycogen A short segment of amylose. An (α1→6) branch point of glycogen or amylopectin . but has more branching than amylopectin. Amylopectin has stretches of similarly linked residues between branch points. Glycogen Glycogen has the same basic structure as amylose. a linear polymer of D-glucose residues in (α1→4) linkage.

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Cellulose Human enzymes can digest a1­4 but not b1­4 glycosidic linkages Cellulase in microbes can breakdown b1­4 linkages (Ruminants have microbes in stomach) .

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.A short segment of chitin. a homopolymer of N-acetyl-D-glucosamine units in (β1→4) linkage.

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Membrane proteoglycan .

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Cell-extracellular interaction .

Glycoproteins .

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 They have the H antigen AB blood group individuals have both A and B antigens on their RBCs and no antibodies in their serum. Individuals possessing the A antigen on the surface of their red blood cells (RBCs) are said to have the A  blood group. A and B.Blood groups The ABO blood group system comprises two antigens. They also have anti­B antibodies in their serum. .  O blood group individuals have neither A nor B antigen on their RBCs but they do possess anti­A and  anti­B antibodies in their serum.  Individuals possessing the B antigen on the surface of their RBCs are said to have the B blood group.  They have anti­A antibodies in their serum.

 Landsteiner. If they belong to different groups the blood cells will clump.ABO blood groups The Human A.  The 4 blood types were defined on the basis of a clumping reaction.O blood groups were discovered in 1900 by Dr.  Serum (the liquid part of the blood (Ab)) from one individual is mixed with red blood cells (erythrocytes) from  another individual. Blood group  A Genotype  IAIA IAi An on RBC  A  Ab in blood  B B  IBIB IBi B  A AB IAIB AB ­ O ii  ­  A B  61 .B. The clumping is due to the presence  of antibodies in the serum.

N-acetyl glucosamine D-galactose To this precursor substance is added the terminal sugar. This H antigen is a precursor of ABO blood group antigens. The substance thus formed is called H antigen. Each molecule is made up of a peptide backbone the band 3 protein. which is the anion  exchange protein of the RBC membrane. L-fucose.A and B antigens are basically glycoproteins. D-galactose. Attached to the protein from inside out are: N-acetyl galactosamine. .

  The B allele encodes a glycosyltransferase that joins α­D­galactose bonded to D­galactose end of  H antigen.  The A allele encodes a glycosyltransferase that bonds α­N­acetylgalactosamine to D­galactose end  of H antigen. The ABO locus has three main alleleic forms: A. producing the A antigen. and O. . the exon 6 of the gene contains a deletion that results in a loss of enzymatic  activity.The ABO gene is located on chromosome 9. In case of O allele. creating the B antigen. B.

 This change gives rise to the B  specificity.In case of individuals having AB blood group. the largest of all.  .  There are seven exons for the ABO enzyme Seven nucleotide substitutions distinguish the A transferase from the B  transferase One substitution is in exon 6. two different sugars. so that a smaller size  UDP­Gal. becomes preferentially  accommodated as a substrate.  This is because those two sites reside at the active site of the enzyme In the A enzyme L  and G are present in the active site In the B enzyme M and A are present in the active site. contains the  other six nucleotide substitutions. or the B enzyme. rather than UDP­GalNAc. exon 7. N­ acetyl galactosamine and D­galactose. are transferred to different  chains of the same RBC. This results in  an alteration of the shape of the active site pocket.   These result in four amino acid substitutions that differentiate the A  and B transferases.  Substitutions at two sites (L 266M and G268A) determine the A or B  specificity of the enzyme.